Thermosetting polyester powder coating compositions

ABSTRACT

1. A THERMOSETTING COATING COMPOSITION IN THE FORM OF A POWDER HAVING AN AVERAGE PARTICLE SIZE RANGE OF FROM ABOUT 10 TO ABOUT 300 MICRONS COMPRISING (A) A POLYESTER DERIVED FROM A DICARBOXYLIC ACID COMPONENT, AT LEAST 50 MOLE PERCENT OF WHICH IS TEREPHTHALIC ACID OR ISOPHTHALIC ACID, A GLYCOL COMPONENT, AT LEAST 50 MOLE PERCENT OF WHICH IS NEOPENTYL GLYCOL, AND FROM ABOUT 2 TO ABOUT 10 MOLE PERCENT OF A POLYOL CONTAINING FROM 4 TO 16 CARBON ATOMS AND HAVING AT LEAST 3 PRIMARY HYDROXYL GROUPS, (B) FROM ABOUT 2 TO 15 PHR, BY WEIGHT OF A MELAMINE CROSS-LINKING AGENT, AND (C) FROM ABOUT 0.1 PHR. TO ABOUT 3.0 PHR. BY WEIGHT OF THE REACTION PRODUCT OF AN ACID AND A COMPOUND CONTAINING OXIRANE GROUPS, SAID POLYESTER BEING FREE OF APPRECIABLE CROSSLINKING.

United States Patent M 3,842,021 THERMOSEITING POLYESTER POWDER COATING COMPOSITIONS Peter M. Grant, Robert B. Taylor, and Winston J. Jackson, Jr., Kingsport, Tenn., assignors to Eastman Kodak Company, Rochester, NY. No Drawing. Filed Feb. 26, 1973, Ser. No. 335,872 Int. Cl. C08b 21/08; C08g 37/34 US. Cl. 260-15 10 Claims ABSTRACT OF THE DISCLOSURE Thermosetting powder coating compositions comprising a polyester derived from an acid component, at least 50 mole percent of which is terephthalic or isophthalic acid, a glycol component, at least 50 mole percent of which is neopentyl glycol, and from about 2 to about 10 mole percent of a polyol having at least 3 primary hydroxyl groups. The composition further comprises a crosslinking agent and a catalyst which allows the powder to flow out prior to fusion. The coating has excellent physical properties such as gloss, toughness, weatherability, etc.

This invention relates generally to thermosetting powder coating compositions, and more specifically to such compositions comprising a polyester as the main film-forming component.

Plastic materials for powder coatings are classified broadly as either thermosetting or thermoplastic. In the use of thermoplastic powder coatings, heat is applied to the coating onthe substrate, thereby melting the particles of thermoplastic powder. The molten particles flow to gether and form a smooth coating prior to removal of heat, which allows the coating to cool and solidify.

Thermoplastic coatings, however, have several disadvantages compared to thermosetting coatings. Thermosetting coatings generally are tougher, more resistant to solvents,- have better adhesion to metal substrates, and do nottend to soften when exposed to elevated temperatures. On the other hand, thermosetting powder coatings in the past have had a disadvantage in that they cure or set by the application of heat prior to the formation of a smooth coating, resulting in a relatively rough finish, such as the so-called orange-peel appearance, thus lacking the gloss and luster characteristics of thermoplastic powder coatings which are often desirable. This has resulted in thermosetting coatings usually being applied from organic solvent systems, whichis not as desirable as powder coating systems because of the usual fire and health hazards, as well as cost.

It has now been found that when certain polyesters are modified with certain amounts, within a fairly narrow range, of a polyol containing at least 3 primary hydroxyl groups and mixed with conventional crosslinking agents such as aminoplasts, crosslinking will occur under curing conditions. Furthermore, powder compositions containing polyesters modified according to this invention unexpectedly resist caking at normal storage conditions of temperatures up to, say, 80 F. Powder coatings made from compositions containing the modified polyesters according to this invention are found to have excellent physical properties, such as good flow-out capability, good weatherability, resistance to heat, scufiing, moisture and solvents, hardness, flexibility, and excellent impact strength.

It is, therefore, an object of the present invention to provide a noncaking thermosetting powder coating composition which is friable and free-flowing at ambient conditions.

It is another object of this invention to provide a thermosetting powder coating composition which will 3,842,021 Patented Oct. 15., 1974 flow out prior to curing or thermosetting to result in a smooth, glossy coating substantially free of the so-called orange-peel appearance.

It is a further object of this invention to provide a thermosetting powder coating composition having good weatherability and general physical characteristics.

Other objects of this invention will appear herein.

In accordance with this invention, a thermosetting powder coating composition having a particle size of from about 10 to about 300 microns is provided which comprises a polyester, a crosslinking agent, a special catalyst, and optionally a cellulose ester, a plasticizer, an antioxidant, and a pigment or dye. The polyester may be synthesized using conventional condensation polymerization techniques. The composition may be melt-compounded without causing crosslinking to occur and sub sequently solidified and ground to a particle size suitable for forming thin coatings, or spray dried to achieve both compounding and powder.

The polyester component of the composition according to this invention is derived from:

(a) at least mole percent, preferably at least 90 mole percent, isophthalic or terephthalic acid, or a mixture thereof. Up to 50 mole percent of other aromatic dicarboxylic acids, or up to about 10 mole percent of other aliphatic acids or mixtures thereof may be used. Suitable aliphatic dicarboxylic acids are those containing from 4 to 18 carbon atoms such as adipic acid, succinic acid, glutaric acid, sebacic acid, azelaic acid and the like. Also, other suitable aromatic dicarboxylic acids include 2,5- and 2,6-naphthalene dicarboxylic acids.

(b) at least 50 mole percent, preferably at least 75 mole percent, neopentyl glycol. Up to 50 mole percent of other glycols may be used. Several examples of other glyc0ls include 2,2,4-trimethylpentanediol, 1,4-butanediol, ethylene glycol, and cyclohexanedimethanol. (c) from about 2 mole percent to about 10 mole percent of a polyol having from 4 to 16 carbon atoms and containing at least 3 primary hydroxyl groups (preferably from 3 to 8) suchas trimethylol propane, trimethylol ethane, pentaerythritol, dipentaerythritol, etc.

The polyester component is made by conventional condensationpolymerization procedures well known in the art. The inherent viscosity of the polyester is preferably between about 0.1 and 0.4 as determined at 23 C. using 0.5 gram of polymer per 100 ml. of a solvent consisting of a /40 mixture of phenol/tetrachloroethane. Also, the glass transition temperature should be at least 60 C., preferably at least C.

The crosslinking agents of this; invention are well known in the art and many are commercially available. Suitable crosslinking agents include melamine-formaldehyde resins such as butylated melamine-formaldehyde resins such as those sold under the trade names Plaskon 3382, Resimine 879 and Beckamine 1216 -8. A preferred crosslinking agent is hexamethoxymthylmelamine. Cymel 300. is suitable for this use and is available from Ameriwhere R is alkyl, aryl, or aryloxy from C -C and R R and R are each hydrogen, alkyl from C to C or phenyl. Preferably, the compound is bisphenol A bisglycidyl ether or its low polymers commercially available from Shell Chemical Company under the trade name Epon resins, and R R and R are each hydrogen. Such a catalyst is described in a copending application of Parsons and Sheme filed Feb. 26, 1973, Ser. No. 335,870 said application being assigned to the same assignor as this application. j i v The temporary deactivation of the acid catalyst is thought to occur through the oxirane group tying up the acid group which can later be freed or reactivated through the application of heat. To produce the temporarily deactivated catalyst, the acid catalyst and the epoxy compound are mixed in about stoichiometric proportions and allowed to stand for a sufficient period of time to assure that a complete reaction has occurred. Once the reaction has occurred the catalyst is in a neutral state.

Another type of epoxy compound that is a good source of the oxirane group for use in forming the temporarily deactivated acidic catalyst is sold under the trade name Epoxol 9-5. Obviously, other materials or oils could be used as long as they will furnish an oxirane group for reacting with the acidic catalyst to form the desired reversible, normally neutral catalyst product. Also, substituted oxirane compounds such as ethylene oxide or propylene oxide may be used. A commercially available resin is Epon 812 marketed by Shell Chemical Company.

Although p-toluenesulfonic acid is preferred as the base acid from which the blocked catalyst is to be formed, it should be realized that other aromatic acids which will react properly with an oxirane group and can later be restored to an acidic or active condition by heating for promoting a reaction between the crosslinking agent 'and polyester could be used. Examples of other acids which can be used are: phenyl acid phosphate, butyl acid phosphate, oxalic acid, benzenesulfonic, and monobutyl 'acid maleate.

It is desirable to conduct the blocking of the catalyst in a mixture containing an inert ingredient as a solvent in order to limit the rate of the blocking reaction. If the reaction is too vigorous, a greatdeal of heatis evolved, and, in the absence of solvent, the temperature mayreach' a point when the oxirane component will either evaporate from the reaction vessel or will polymerize into a gel. The blocked catalyst does not appear to. unblock at temperatures-below about 290 F. with any appreciable rate. Oxirane compounds appear to react with p-toluenesulfonic acid. to cause the acid to become inactive until such a'timeas it is heated above about-290 F. 1 It is believed that anacid, HB, reacts with a compound containing-an oxirane structure to form a beta hydroxy ester of the acid. That is, the following reaction occurs which results in the formation of the blocked catalyst:

R R R and R are as defined hereinbefore. B represents the anion of the acid used for catalysis.

ene oxide the reaction is believed to be:

In the specific case of p-toluenesulfonic acid and propyl- When heated above about 290 .F.,..,this reaction is apparently reversed, allowing the free acid to be formed which thus is available to catalyze the crosslinking of the film. It is apparently only at temperatures above "about 290 F. that this reverse action occurs rapidly enough to cause the crosslinking reaction to take place rapidly. It is desirable for the thermosetting powder coating composition of the present invention to also include a cellulose ester such as cellulose acetate butyrate. The preferred cellulose ester has a butyryl content of between about 30 and about 55% by weight, a 'hydroxyl'content of between about 0.1 and about 5% by'weight, an'acetyl of about 1 to 15%, (measured asapercentage of the total weight of one auhydroglucose unit) and a viscosity of from 0.01 to 20 seconds (ASTM 'D-817-65 Formula A and D-1343-56). a c

The thermosetting powder coating composition may also contain a suitable plasticizer. The plasticizer must be sufiiciently compatible to avoid a sticky formulation. Suitable plasticizers include dioctyl phthalate, di butyl phthalate, butyl benzyl phthalate, 2,2,4-trirnethylpentanediol- 1,3-monoisobutyrate monobenzoate, trioctyl trimellitate, an ester derived from neopentyl glycol and adipic acid, or the like. I v

Conventional stabilizers, such as Irganox 1093, a product of Ciba-Geigy, may be used in small amounts to prevent discoloration, etc. Also, conventional dyes or pigments such as R- titanium dioxide pigment marketed by Du 'Pont may be used. I The components of the powder coating compositions according to this invention may be mixed by dry blending in a mixer or blender (e.g., a Waring Blender), followed by compounding in a Braben-der Extruder at C. and 50400 r.p.m., granulating, cryogenically grinding and thenscreening to obtain a mesh powder for coating. Also, the polyester and celluloseester, pigment and stabilizer, if used, may be extruded at'about 200 C., then mixed with the crosslinking agent catalyst, and plasticizer (if used) in a Banbury mixer, a'combination of a Banbury mixer and roll mill, a roll mill alone or an extruder at a temperature ofbetween about, l0 0.'. C. and 150 C. Alternately, all the components may be dissolved in a solvent such as methylene chloride (atabout 2.0 .weightpercent solids) and spray dried ata chambertemperature of about 50 C. by well-known techniques...

,;The powdered, composition may be deposited on. the substrate by use of v a powder gun, by electrostatic deposition or by deposition from afluidized bed or by; other well-known methods of powder deposition. Afterdeposi tion the .powder is heated to a temperature sufiicient-zto' cause its particles to flow audthus fuse together toiform a smooth, uniform, continuous, uncratered coating 'on thefisubstrate surface. Normally, temperatures of'a'round 350 F.375". F. are required for curing.

The following examples are submitted for a better un-' derstandingof the invention.

In the examples, the physical properties of the coatings are determined as follows: l

I i Appearance Rating -:--In order to obtain appearance as anumerical value for identification, the following rating system for orange peel appearance and crater evaluation is used:

8-None 3-Moderate 7-Trace 2-Moderate to heavy 6-Very slight l-Heavy S-Slight O-Very heavy 44light to moderate Adhesion Tape Test Seven horizontal score lines about 7 6 inch apart are crossed with seven vertical score lines about V inch apart using a sharp razor blade to cut through the coating to the metal. Pressure sensitive tape (Scotch) is pressed down firmly over the cross-hatched pattern and pulled off rapidly. A complete failure is recorded when the coating is completely peeled off. A partial failure is noted when 5 squares or more are lifted and a slight failure is identified when less than five squares are lifted. When the coating is brittle, as may occur from degradation, it does not have the cohesive strength to peel, and hence splits next to the score line giving an apparent appearance of good adhesion since the bulk of the coating is not removed. It is necessary to examine the tape and the coating for signs of such behavior being due to brittleness and not adhesion.

Acetone Resistance The softening of the coating caused by acetone being applied to the surface is determined.

Caking at 80 F.

Samples of 3-5 grams are placed in a container and allowed to age for a selected time (usually 48 hours) at the indicated temperature. The samples are then inverted and inspected visually for caking.

Impact Strength Impact strength is determined by using a Gardner Laboratory, Inc., Impact Tester. A weight is dropped within a slide tube from a specified height to hit a punch having. a inch diameter hemispherical nose which is driven into the front (coated face) or back of the panel. The highest impact which does not crack the coating is recorded in inch-pounds, front. and reverse.

Flexibility The test panel is bent over a period of 15 seconds, using a Gardner Laboratory, Inc., conical mandrel of specified 6 Gloss Twenty degree and sixty degree gloss are measured using a gloss meter (Gardner Laboratory, Inc., Model GC-9095) according to ASTM D-523.

Pencil Hardness The pencil hardness of a coating is that of the hardest pencil that will not cut into the coating. The procedure for preparing the truncated cone pencil lead and carrying out the test is given in the National Coil Coaters Association Technical Bulletin No. II (Aug. 12, 1968). Results are expressed according to the following scale:

(softest) 6B, 5B, 4B, 3B, 2B, B, HB, F, H, 2H, 3H, 4H,

5H, 6H (hardest) Weatherability The loss of gloss, change in impact strength, and flexibility are determined following a specified time of being subjected to artificial weather conditions.

Coating Thickness The coating thickness is determined using a General Electric Thickness Gauge, Type B.

Fusion of the Coating Test panels are placed in a Freas Model 625A forced air oven and fused at a specified temperature for a specified time. The fused coatings are then hung on a bar to cool at room temperature.

In Examples 1 through 21, polyesters are prepared by conventional techniques from dimethyl terephthalate, neopentyl glycol and varying levels of trimethylolpropane and inherent viscosities, a specific example of which is as follows:

Into a 1000-ml. flask are placed 400 g. of the polyester (I.V. about 0.7) and the desired amount (1-10 mole percent) of the triol. After the flask is equipped with a stirrer and provision for maintaining a nitrogen atmosphere, it is then immersed in a metal heating bath which is maintained at 225 C. for 3-4 hours. During this period, the contents of the flask, under nitrogen, are stirred continuously, slowly at first and more rapidly later as the glycolysis reaction occurs and the melt viscosity of the polyester decreases. The hydroxylated poly ester has an inherent viscosity of about 02-03, depend;

ing on the amount of triol added. Inherent viscosities are A determined at a concentration of 0.5 g./100 ml. in 60/40 phenol/tetrachloroethane at 23 C.

size,. according to ASTM D-522. A pass or fail is re- The polyesters so prepared are mixed with 10 phr. crosscorded. linking agent (hexamethoxymethylmelamme), 5 phr. Ko-.

TABLE I Appearance Fusion rating Impact strength temp. Thick- Adhesion in.-lb. Flexibility Gloss Caking F., for ness, Orange De conical Pencil at room I.V. 10 min. mil. peel Crater test Front Reverse mandrel 20"v hardness temperature 0.29 325 1.3 6 10 Fail 0.29 350 1.4 6 0.29 375 1.3 6 0.29 400 1.3 6 0.29 425 1.1 6 0.29 450 1.0 6 0.29 475 0.8 6

Slight yellowing 2.5 0.26 325 1.3 2.5 0.2 350 1.3 6 2.5 0.26 375 1.1 6 2.5 0.26 400 1.1 6 2.5 0.26 425 0.7 6 2.5 0.26 450 1.0 6 2.5 0.26 475 0.9 6

Slight I yellowing 10 0 28 325 1.4 6

10 0. 28 350 1.3 6 10 0.28 375 1.4 6 10 0. 28 400 1.4 6 10 0.28 425 1.2 6 10' 0.28 450 1.0 6 20 d 10 0.28 475 0.8 6 10 FaiL- Slight yellowing .7 8 daflex NP-10 (an alcohol terminated polyester of neoprepared as in Examples 1 through 21, except the con: pentyl glycol and adipic acid marketed by Eastman Chemicentration of crosslinking agent (hexamethoxyme'thylmelcal Products, Inc., 10 phr. cellulose acetate butyrate EAB amine) is varied, the level of trimethylolpropane is held at 51-02 having a viscosity of 0.15-0.30 seconds as measand no catalyst is used. The thickness of the coatings ured by ASTM D-817-65 (Formula A) and D-1343-56, is between 1.0 and 1.4 mil. The results are given in Table an acetyl content of about 2% by weight, a butyryl con- 5 II.

TABLE II Impact Appearance strength Cross- Fusion rating in.1b. linking temp., Adhesion Flexibility Gloss Caking agent, F.,for Orange tape Re- 5 conical Pencil v atroom phr. I.V. 10min. peel Crater Front verse mandrel 60 hardness temperature tent of about 53% by ight and a hydroxyl content of 30 In the following Examples 43 through 70, compositions about 1.6% by weight, and 40 phr. R-l00 T10 pigment. are prepared as in Examples 1 through 21, holding the The catalyst is P p from 1 P of a 131 Solution of concentration of crosslinking agent (hexamethoxymethylp-toluenesulfomc acid and n-butanol and 4 parts Epon 812, melamine) at 10 phr and the level of trimethylol-pmpane a glycerol epichlorohydrin type epoxy resin sold by Shell Chemical Company, orabisphenolAepichlorohydrin type 35 at but varifmg F f? the catalyst epoxy resin and i used i an amount f 1 The The results are given 1n Table III contammg Examples components are prepared by dry blending in a Waring 43 through 70.

TABLE III Appearance I r Fusion rating Impact strength Catatemp. Thickin.lb. Flexibility Gloss Cakmg at 1 lyst, F., for ness, Orange Adhesion 3 conical Pencil room temphr. I.V. 10min. mil. peel Crater tape test Front Reverse mandrel 60 hardness perature f 0 0.28 325 1.3 6 1 7 20 0 0.28 350 1.0 6 7 0 0. 28 375 1.0 6 7 None. 0 0.25 400 0.9 6 7 50 0 0.28 425 0 9 6 7 160 0 0.28 450 1.0 6 7 160 0 0.28 475 0.8 6 7 140 Shght yellowing 0.75 0.28 325 1 2 6 .7 20 V N 0.75 0.28 350 1.4 6 7 40 0.75 0.23 375 1.4 6 8 160 Do. 0.75 0.23 400 1.0 6 7 160 0.75 0.28 425 1.0 6 8 160 075 0.28 450 1.0 6 7 160 0.75 0.28 475 0.9 6 7 Slight yellowing 1.5 0.28 325 1.4 6 8 30 1.5 0.28 350 1.3 6 8 40 1.5 0.28 375 1.4 6 8 160 Very slight 1.5 0.28 400 1.4 6 8 160 1.5- 0.28 425 1.2 6 8 160 1.5 0.28 450 1.0 6 s 1.5 0.28 475 0.8 6 7 40 Slight yellowing 3.0 0.28 325 1.7 6 8 40 3.0 0.28 350 1.3 6 160 3.0 0.23 375 1.4 6 160 3.0 0.28 400 1.4 6 160 3.0 0.23 425 1.5 6 160 3.0 0.28 450 1.2 6 50 3.0 0.23 475 1.1 6 8 F 50 Slight yellowing Blender followed by compounding m a Brabender EX- In the followmg Examples 71 through 82, compos1- truder C.- C. and'50-100 r.p.m.), granulatlng, tlons are prepared as in Examples 1 through 21, holding cryogemcally grinding and then screemng to obtain a the concentratlons of crosslmkrng agent (hexamethoxymesh powder for electrostatic spray onto steel test panels. methylmelamine) at 10 phr., the level of trimethylolpro- After the'coating's are applied to test panels, the coatings pane at 10%, no curing catalyst, but varying the concenare heated at the indicated temperatures for 10 minutes. tration of cellulose acetate butyrate (EAB 551-02). The The results are given in Table I containing Examples 1 results are given in Table -IV containing Examples 71 through 21. f through 82. Five phr. plasticizer (ester of neopentyl glycol In the Examples 22 through 42, compositions are and adipic acid) are used in each of these examples. I?

TABLE IV Appearance Impact Cellulose rating strength acetate Fusion Thickin.-lb. Flexibility Gloss Gaking butyrate temp, F., ness, Orange Adhesion $4 conical Pencil at room level phr. for 10 min. mil. peel Crater tape test Front Reverse mandrel 20 60 hardness temperature 425 1.3 6 10 Pass 40 84 0 450 1. 1 6 72 Moderate. 0 475 1. 0 6 5 425 1.2 6 5 450 1.3 6 5 475 1. l 6 425 1.3 6 10 450 1.1 6 10 475 1. 2 6 425 1.4 7 20 450 1.5 7 20 475 1. 5 7

50 phrIR-lOO TiO pigment. The'composition is of a size of 150 mesh and is coated on a bonderized steel plate using an electrostatic spray gun. When about 2% pentaerythritol is substituted for the 5% trimethylolpropane, and about the same amount of hexabutoxymethylmelamine is substituted for the hexamethoxymethylmelamine, similar results are obtained in Examples 83-95.

trations, therefore, of between about 0.1 phr. and about 3 phr. may be used, with about 1.5 phr. being preferred. The results illustrate the effects of poor crosslinking at temperatures below about 350 F., as well as adverse eliects above about 450 F.

Cellulose esters, particularly cellulose acetate butyrate, .are desirable components of the composition as they reduce caking tendencies and improve the ability of the powder coating to flow out when subjected to heat and become smooth. Concentrations of up to 20 phr. of cellulose acetate butyrate are desirable, while above about 20 phr., there is a tendency for the cellulose acetate butyrate to become incompatible with the polyester. A concentration of about 10 phr. cellulose acetate butyrate as defined herein is preferred.

TABLE V Appearance rating Impact strength 7 Fusion Thiek- Adhesion in.-lb. Flexibility Gloss temp, F., ness, Orange tape /g" conical Pencil Acetone Example for 10 min. mil peel Crater test Front Reverse mandrel 20 60 hardness resistance 325 1. 3 6 16 350 1. 1 6 12 375 1. 0 6 13 400 1. 0 6 18 425 1. 1 6 18 450 1. 1 e 2a 475 1.1 Very slight yellowing uhdo 21 375 0. 8 2

Incomplete covering 375 1. 2 6 15 375 1. 5 6 18 375 2.4 7 10 375 3. 6 Textured 1 375 i 5. 5 Textured 8 do'. 2

The results illustrated in the examples indicate that the polyester component of the formulation should contain the lowest level of polyol modification possible without loss of coating properties, as increasing the polyol content above about 10 mole percent increases the caking tendency of the composition. Between about 2 mole percent and about 10 mole percent of the polyol should be used with about 5 mole percent being preferred. Below about 2 mole percent, insuflicient crosslinking occurs. Also, the results indicate that the concentration of the crosslinking agent should be maintained between about 2 phr. and about 10 phr., with about 7.5 phr. being preferred, when the level is increased above about 10 phr., the tendency for the powder to cake increases. Caking of the powder cannot be toleratedbecause of application .difiiculties as well as coating thickness considerations.

Tables II and IV illustrate caking tendencies and also show that a formulation containing no curing catalyst requires a curing temperature of greater than 400 F. for 10 minutes to obtain good impact strength and flexibility. Excessively high curing temperatures are often undesirable as some substrates cannot withstand these heating conditions and more energy is required. The formulations containing the catalyst have adequate curing at about 350-375 F. for 10 minutes, and still the coating flows out to form a smooth coating prior to crosslinking. Compositions containing above about 3 phr. catalyst have a tendency to cake at room temperature. Catalyst concenmelamine), 1.0 phr. catalyst as described for Examples 1-21, 10 phr. cellulose acetate butyrate (EAB 551-02), 5 phr. plasticizer (Kodaflex NP-lO), 0.5 phr. Irganox 1 093 stabilizer, and 50 phr. R-100 TiO The polyester has al I.V. of 0.29 and a glass transition temperature of 68 Examples 89-94 illustrate powder coating compositions comprising a polyester, 10 phr. crosslinking agent (hexamethoxymethylmelamine), 1.5 phr. catalyst, 10 phr. cellulose acetate butyrate, 5 phr. plasticizer (Kodaflex NP-lO), 0.5 phr. Irganox 1093 and 40 phr. TiO .The polyester is derived from terephthalic acid, 50 mole percent ethylene glycol and 50 mole percent neopentyl glycol modified with 5 mole percent trimethylolpropane. It has an I.V. of 0.20 and a glass transition temperature of 65 C. Examples -99 illustrate powder coating composi: tions as described for Examples 89-94, except the polyester is derived from 50 mole percent terephthalic acid,

50 mole percent isopthalic acid and ethylene glycol modified with mole percent trimethylolpropane.

cyclohexanedimethanol modified with 5% trimethylolpropane, having an I.V. of 0.36.

TABLE VI Exposure Appearance rating Impact strengthin.-lb.

time in Fusion weathertemp., F. Thickness, Orange Flexibility /s Adhesion, scotch Example ometer hours minutes mils. peel Crater Front Reverse conical mandrel tape 0 400 1.7' 6 8 160 Pass. 100 400 1.4 6 s 120 Do. 300 400 1.6 6 s so Do. 500 400 1.7 6 8 80 Do. 750 400 1.7 6 8 60 Do. 1,000 400 1.6 6 8 40 D0. 0 400 1.1 6 8 160 Do. 100 400 1.2 6 s 120 Do. 300 400 1.1 6 s 100 D0. 500 400 1.2 6 8 80 Do. 750 400 1.3 6 8 70 Do. 1, 000 400 1. 2 6 s 70 Do. 0 400 1.7 6 s 130 Do. 300 400 1.6 6 s 50 Do. 500 400 1.6 6 s 40 Do. 750 400 1.7 6 8 Do. 1,000 400 1.6 6 s Do.

The above Table VI illustrates the efiect on impact TABLE VII strength and flexlbillty after being sub ected to weather- A 951131108 ab1l1ty tests, where a mixture of mole percent ethylene 35 Gardner gloss a glycol and 50 mole percent neopentyl glycol are used t Fu si gn Thick- 0 em mass range m the polyester of Examples 89-94, and where the glycol Example 10 glinute mils: 6 6 peel Crater component is entirely ethylene glycol 1n Examples -99. 4 6 There is a marked decrease in impact strength and flexi- {g :3 $3 6 '3 bility shown in Examples 95-99. 400 1.3 32 76 6 8 15 8 it Si 38 2 S The weather testing instrument used is described as: 350 0:0 24 69 6 8 Atlas Weather-Ometer, Model 600WRC, Serial No. 2&8 8-3 2g 2 g XE:343:1ight source; xenon burner, 6000 watts; black 425 0.9 25 65 6 7 panel temperature=l45 F.; dry bulb temperature: :28 2-8 32 2% g 113 F., relative humidity=65%; spray cycle=9 min. 233 2.3 g 23 g .7 '7 wet, 51 rmn. dry. 425 1'0 24 63 6 7 450 0.9 I 27 7 69 6 7 In Table VII which follows, each of the examples cono 1 Rmgh 375 1.0 0 3 Rough tains a polyester, 7.5-l0 phr. crosslmkmg agent, 1.0-1.5 400 0.9 2 15 Rough phr. catalyst, 10 phr. cellulose acetate butyrate, 5 phr. fig 8-8, 3 2% 1 g plasticizer, 0.5 phr. Irganox 1093 and 40-50 phr. TiO 350 115 12' 45 r '7 '8 In Examples through 104, the polyester is derived 2E3 i? i g from terephthalic acid and neopentyl glycol modified 425 1.3 11 12 4 s with 5 mole percent trimethylolpropane, has an I.V. of .328 {g i3 g 3 0.29 and a glass transition temperature of 68 C. In Ex- 375 1.3 8 42 5 8 amples through 109, the polyester is derived from 13; {g 2 g? 2 g terephthalic acid, 50 mole percent ethylene glycol, 50 450 1.9 3 19 4 8 mole percent neopentyl glycol and 5 mole percent trimethylolpropane, has an I.V. of 0.20 and a glass transition'temperature of 65 C. In Examples through 114, the polyester is derived from terephthalic acid, isophthalic acid and ethylene glycol, modified with 5% trimethylolpropane, having an I.V. of 0.21 and a glass transition temperature of 61 C. In Examples through 119, the polyester is derived from terephthalic acid, 50 mole percent ethylene glycol and 50 mole percent 1,4-cyclohexanedimethanol modified with 5% trimethylolpropane, having an I.V. of 0.24 and a glass transition temperature of 63 C. In Examples through 124 the polyester is derived from 67%. terephthalic acid, 33% isophthalic acid, and 1,4-cyclohexanedirnethanol modified with 5% trimethylolpropane, and having an I.V. of 0.34 and a glass transition temperature of 72 C. In Examples 125 through 129, the polyester is derived from 60 mole percent terephthalic acid, 40 mole percent isophthalic acid and 1,4-

From the above Table VII containing Examples 100 through 129, it will be noted that polyesters derived from neopentyl glycol have a much better gloss rating and appearance rating than polyesters derived from 1,4-cyclohexanedimethanol. I

Considering Tables VI and VII, a comparison is given of powder coating compositions derived from polyester based on neopentyl glycol, modified with "a small percentage of polyol, and powder coating composition derived from other glycols also modified with a small percentage of polyol. A comparison of the physical properties of the coatings reveals that powder coating compositions derived from polyester containing at least 50 mole percent neopentyl glycol results in a unique combination of proper ties not provided by other polyesters. d

In Examples through 138, powder coating compositions are prepared using a polyester, 7.5 phr. cross- 13 linking agent, 1.0 phr. catalyst, 10 phr. cellulose acetate butyrate EAB 551-02, 5 phr. Kodafiex NP-lO, 0.5 phr. Irganox 1093 and 50 phr. R100 T10 The polyester is prepared from terephthalic acid and neopentyl glycol. In Examples 130 through 132, the polyester is modified 5. A thermosetting coating composition according to claim 1 wherein said reaction product is the reaction product of an aromatic sulfonic acid and a compound containing oxirane groups.

6. A thermosetting coating composition according to with 5% glycerin, and in Examples 136 through 138, the 5 claim 1 which comprises from about 5 to about 20 phr. polyester is modified with 5% trimethylolpropane. The cellulose acetate butyrate based on the weight of said physical properties of the coatings are shown in Table polyester. VIII. 7. A thermosetting coating composition according to TABLE VIII Appearance Impact- Gardner rating strength Fusion Thickgloss in.-lb. Flexib lity Adhesion temp., ness, Orange Conical Pencil Acetone 10 minutes mils 20 60 peel Crater Front Reverse mandrel hardness Scotch tape Peel resistance 350 2.0 43 7s 6 s 20 10 Fail Fail Pass. Poor. 375 1.7 22 e2 6 8 80 30 Pass F Pass do Fair. 400 1.5 23 63 e 8 80 Good. 350 1.3 16 55 7 7 50 Poor. 375 1.0 24 as 7 7 80 400 1.2 25 71 6 7 80 Fall. 350 1.1 12 45 e s 50 375 1.0 13 50 6 8 160 do Good 400 1.0 18 s 6 8 160 It will be seen from Table VIII that the coatings prepared from compositions containing the polyols having only primary hydroxyl groups, e.g., trimethylolpropane, have significantly superior properties to those containing the secondary hydroxyl groups, e.g., glycerin. Examples 133-135 illustrate the efiects of the polyester containing no polyol modification.

Unless otherwise specified, all parts, percentages, ratios, etc., are on a weight basis. The term phr. is a conventional term in the art meaning parts per hundred parts resin, where resin referred to herein is the polyester. Also, use of the term acid herein is intended to include anhydrides where the acid has an anhydride.

Although the invention has been described in considerable detail with particular reference to certain preferred embodiments thereof, variations and modifications can be effected within the spirit and scope of the invention.

We claim:

1. A thermosetting coating composition in the form of a powder having an average particle size range of from about to about 300 microns comprising (a) a polyester derived from a dicarboxylic acid component, at least 50 mole percent of which is terephthalic acid or isophthalic acid, a glycol component, at least 50 mole percent of which is neopentyl glycol, and from about 2 to about 10 mole percent of a polyol containing from 4 to 16 carbon atoms and having at least 3 primary hydroxyl groups,

(b) from about 2 to 15 phr. by weight of a melamine cross-linking agent, and

(c) from about 0.1 phr. to about 3.0 phr. by weight of the reaction product of an acid and a compound containing oxirane groups, said polyester being free of appreciable crosslinking.

2. A thermosetting coating composition according to claim 1 wherein the polyester contains at least 90 mole percent isophthalic acid or terephthalic acid and at least 75 mole percent neopentyl glycol.

3. A thermosetting coating composition according to claim 1 wherein the polyester contains between about 4 and 8 mole percent of a polyol having from 4 to 16 carbon atoms and between 3 and 8 primary hydroxyl groups.

4. A thermosetting coating composition according to claim 1 wherein the melamine crosslinking agent is hexaalkoxymethylmelamine wherein the alkoxy group contains from 1 to 20 carbon atoms.

claim 1 wherein said polyester has an inherent viscosity of between about 0.1 and about 0.4.

8. A thermosetting coating composition according to claim 1 wherein said polyester has a glass transition temperature of at least about 65 C.

9. A thermosetting coating composition according to claim 1 wherein said powder has an average particle size of from about 20 to about 50 microns.

10. A thermosetting coating composition in the form of a powder having an average particle size of between about 10 and about 300 microns comprising (a) a polyester derived from a dicarboxylic acid component, at least about 90 mole percent of which is isophthalic or terephthalic acid, a glycol component, at least about mole percent of which is neopentyl glycol, and from about 2 to about 10 mole percent of a polyol containing from 4 to 16 carbon atoms and having at least 3 primary hydroxyl groups, said polyester having an inherent viscosity of from about 0.1 to about 0.4 and a glass transition temperature of at least about 65 C.,

(b) from about 2 to about 15 phr. by weight of a hexaalkoxymethylmelamine crosslinking agent wherein the alkoxy group contains from 1 to 20 carbon atoms, and

(c) from about 0.1 phr. to about 3.0 phr. by weight of the reaction product of an aromatic sulfonic acid and a compound containing at least one oxirane group, said polyester being free of appreciable crosslinking.

References Cited UNITED STATES PATENTS 3,759,854 9/1973 Chang et a1. 260850 3,684,565 8/1972 Psencik 260850 3,039,979 6/1962 Carlick et al 26'0850 3,265,645 8/1966 Coney et a1 26015 MELVIN GOLDSTEIN, Primary Examiner E. WOODBERRY, Assistant Examiner US. Cl. X.R.

117-132 A, B, BF, 161 C, K, 161 LN, 166; 260850 

1. A THERMOSETTING COATING COMPOSITION IN THE FORM OF A POWDER HAVING AN AVERAGE PARTICLE SIZE RANGE OF FROM ABOUT 10 TO ABOUT 300 MICRONS COMPRISING (A) A POLYESTER DERIVED FROM A DICARBOXYLIC ACID COMPONENT, AT LEAST 50 MOLE PERCENT OF WHICH IS TEREPHTHALIC ACID OR ISOPHTHALIC ACID, A GLYCOL COMPONENT, AT LEAST 50 MOLE PERCENT OF WHICH IS NEOPENTYL GLYCOL, AND FROM ABOUT 2 TO ABOUT 10 MOLE PERCENT OF A POLYOL CONTAINING FROM 4 TO 16 CARBON ATOMS AND HAVING AT LEAST 3 PRIMARY HYDROXYL GROUPS, (B) FROM ABOUT 2 TO 15 PHR, BY WEIGHT OF A MELAMINE CROSS-LINKING AGENT, AND (C) FROM ABOUT 0.1 PHR. TO ABOUT 3.0 PHR. BY WEIGHT OF THE REACTION PRODUCT OF AN ACID AND A COMPOUND CONTAINING OXIRANE GROUPS, SAID POLYESTER BEING FREE OF APPRECIABLE CROSSLINKING. 